JP2017532379A - Method - Google Patents

Abstract

Providing a reaction mixture comprising an alkene and carbon tetrachloride in the main alkylation zone to produce a C3-6 chlorinated alkane in the reaction mixture; extracting a portion of the reaction mixture from the main alkylation zone; A) a method for producing a C3-6 chlorinated alkane comprising the steps of: a) determining the concentration of C3-6 chlorinated alkane in the reaction mixture in the main alkylation zone, ~ 6 alkanes: carbon tetrachloride is maintained at a concentration that does not exceed a 95: 5 molar ratio when the primary alkylation zone is in continuous operation and / or b) is extracted from the primary alkylation zone The reaction mixture additionally comprises an alkene, from which at least about 50% by weight or more of the alkene present in the reaction mixture is extracted, and at least about 50% of the extracted alkene is extracted. Subjected to a dealkenylation step in which 0% is returned to the reaction mixture fed to the main alkylation zone and / or c) the reaction mixture present in the main alkylation zone and extracted from the main alkylation zone is additionally catalyzed An aqueous process wherein the reaction mixture extracted from the main alkylation zone is contacted with an aqueous medium in the aqueous treatment zone to form a biphasic mixture and the organic phase containing the catalyst is extracted from the biphasic mixture Disclosed is a method for use in the process. [Selection figure] None

Description

The present invention, tetrachloropropane, pentachloropropane, pentachlorobutane, and a manufacturing method of high purity C _{3 ~ 6} chlorinated alkane compounds of such hepta-chloro hexane, to compositions comprising a compound according to the list.

  Haloalkanes have found use in a wide range of applications. For example, halocarbons are widely used as refrigerants, blowing agents, and foam agents. Throughout the second half of the 20th century, the use of chlorofluoroalkanes increased dramatically until the 1980s when concerns about their environmental impacts, especially the depletion of the ozone layer, were raised.

  Since then, fluorinated hydrocarbons such as perfluorocarbons and hydrofluorocarbons have been used in place of chlorofluoroalkanes, but recently environmental issues have arisen with the use of this type of compound to reduce its use. The law was enacted in Europe.

  New types of environmentally friendly halocarbons have emerged and have been studied and in some cases have been adopted in many applications, especially as refrigerants in the automotive and household sectors. Examples of such compounds include 1,1,1,2-tetrafluoroethane (R-134a), 2-chloro-3,3,3-trifluoropropene (HFO-1233xf), 1,3,3,3 -Tetrafluoropropene (HFO-1234ze), 3,3,3-trifluoropropene (HFO-1243zf), and 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,2,3 3,3-pentafluoropropene (HFO-1225ye), 1-chloro-3,3,3-trifluoropropene (HFO-1233zd), 3,3,4,4,4-pentafluorobutene (HFO-1345zf) 1,1,1,4,4,4-hexafluorobutene (HFO-1336mzz), 3,3,4,4,5,5,5-heptafluoropentene ( FO1447fz), 2,4,4,4-tetrafluorobutane-1-ene (HFO-1354mfy) and 1,1,1,4,4,5,5,5-octafluoropentene (HFO-1438mzz). It is done.

  Relatively speaking, while these compounds are not chemically complicated, it is difficult to synthesize them on an industrial scale to the required purity. Many synthetic routes proposed for such compounds frequently use chlorinated alkanes or alkenes as starting materials or intermediates. Historically, many of the processes developed for the production of such compounds involved the addition of chlorinated alkanes to fluorinated olefins. However, it has been found that such a process is not acceptable efficiency and results in the production of many impurities. More recently developed processes are typically more direct, chlorinated alkanes or alkene starting materials or raw fluorinated target compounds using hydrogen fluoride and transition metal catalysts such as chromium-based catalysts Including conversion to.

  If the chlorinated feedstock is obtained from a multi-step process, especially if such steps are combined and carried out continuously to reach an industrially acceptable product quantity, cumulative side reactions may occur in each process step. It has been recognized that the need for preventing the production of unacceptable impurities is very important.

  The purity of the chlorinated starting material has a significant impact on the success and feasibility of the preparation process (especially a continuous process) of the desired fluorinated product. The presence of certain impurities will lead to side reactions and minimize the production of the target compound. Also, removal of these impurities is difficult even using the distillation process of the present invention. In addition, the presence of certain impurities impairs catalyst life, for example by poisoning the catalyst.

  In addition, there is a need for an efficient, reliable and highly selective process for preparing high purity chlorinated alkanes and other specialty compounds used in the synthesis of fluorinated compounds referred to above. Several processes for producing purified chlorinated compounds have been proposed in the art (eg US Pat. No. 6,187,978, US Pat. No. 6,313,360, US 2008/091053, US Pat. No. 6,552,238, US Pat. 0171698).

  Despite these advances, problems with the use of chlorinated compounds obtained from the processes discussed above can still arise. In particular, the presence of impurities, particularly impurities that cannot be easily separated from the compound of interest (eg, as a result of similar boiling points) or that reduce the effectiveness or useful life of the catalyst used in downstream processes can be problematic. There is.

  In order to minimize such shortcomings, there remains a need for high purity chlorinated alkane compounds and efficient, highly reliable and highly selective processes for preparing such compounds.

Therefore, a main alkylation zone to produce a C _{3 ~ 6} chlorinated alkane in the reaction mixture giving a reaction mixture containing According to one aspect, the alkene and carbon tetrachloride in the major alkylation zone of the present invention and a extracting a portion of the reaction mixture, a process for the preparation of C 3 _{~ 6} chlorinated alkanes,
a) a major alkylating the concentration of C _{3 ~ 6} chlorinated alkane in the reaction mixture in the zone, C _{3 ~ 6} chlorinated alkanes extracted from the main alkylation zone reaction mixture: four molar ratio of carbon tetrachloride is
Maintained at a concentration not exceeding 95: 5 if the primary alkylation zone is in continuous operation, or 99: 1 if the primary alkylation zone is in batch operation, and / or b ) The reaction mixture extracted from the main alkylation zone additionally comprises an alkene, from which the reaction mixture is extracted from at least about 50% by weight of the alkene present in the reaction mixture, and at least about the extracted alkene is at least about Subject to a dealkenylation step in which 50% is returned to the reaction mixture provided in the main alkylation zone and / or c) the reaction mixture present in the main alkylation zone and extracted from the main alkylation zone is additionally catalyzed And the reaction mixture extracted from the main alkylation zone is contacted with an aqueous medium in the aqueous treatment zone to form a two-phase To form a mixture, the production method of the organic phase containing the catalyst are subjected to an aqueous treatment step of extracting from the biphasic mixture is provided.

The process of the present invention is centered on a highly selective telomerization reaction that is carried out partially or completely in the main alkylation zone. In this reaction, the carbon tetrachloride is reacted with alkenes to produce a C _{3 ~ 6} chlorinated alkanes. While telomerization reaction for producing C 3 _{~ 6} chlorinated alkanes are known in the art, one problem with the process according a production of undesirable impurities, high purity C _{3 ~ 6} chlorinated alkanes There is still a need for a process that ideally and continuously manufactures industrial quantities.

Unexpectedly, also, advantageously, in preparing the C _{3 ~ 6} chlorinated alkanes from alkenes and carbon tetrachloride, one of the steps a) to c) outlined above, some, or by implementing all, higher efficiency (including the reduction of energy consumption), and / or may remove from C _{3 ~ 6} chlorinated alkanes object is difficult, and / or C _{3 ~} It has been found that the formation of impurities, which can be problematic in downstream reactions where ₆ chlorinated alkanes may be used, is minimized. Moreover, surprisingly, the process of the present invention reconciles these advantages including high selectivity and high yield.

  A reaction mixture is formed by contacting the alkene with carbon tetrachloride. This can occur in the main alkylation zone, for example by supplying both alkene and carbon tetrachloride to that zone. Additionally or alternatively, the alkene can be contacted with carbon tetrachloride upstream of the main alkylation zone and then fed to the main alkylation zone.

In an embodiment of the present invention, C _{3 ~ 6} chlorinated alkane in the reaction mixture in a molar ratio of carbon tetrachloride, to control to some numerically defined within limits. In one skilled in the art, such embodiment, while the control process, characterized in this disclosure in terms of the molar ratio of carbon tetrachloride starting material and C _{3 ~ 6} chlorinated alkanes products, production of the starting materials it It will be understood that it can also be considered as a control of the conversion to product (thus the 95: 5 starting material: product molar ratio is equivalent to 5% conversion). The inventors have found that limiting the conversion of the starting material outlined above minimizes the formation of undesirable impurities. In addition, when mentioning that the molar ratio of starting material: product exceeds a given value, this means that a higher degree of conversion of starting material to product, i.e. the proportion of product increases while This means that the proportion of starting material is reduced.

For example, in embodiments of the present invention, a primary alkylation zone can be used upstream of the main alkylation zone. A reaction mixture can be formed by feeding carbon tetrachloride and alkene to the primary alkylation zone to form a reaction mixture fed to the main alkylation zone. In such embodiment, the four partial conversion of carbon tetrachloride to C _{3 ~ 6} chlorinated alkanes of interest, its is alkane formed is included in the reaction mixture fed to the main alkylation zone together with the carbon tetrachloride As can occur in the primary alkylation zone. In additional or alternative embodiments, limits the amount of alkene fed to the primary alkylation zone, the conversion of carbon tetrachloride object C to _3-6 chlorinated alkanes in the primary alkylation zone It can be delayed, so that the reaction mixture supplied therefrom to the main alkylation zone comprises a carbon tetrachloride and C _{3 ~ 6} chlorinated alkanes, including low density or substantially zero alkene.

  Using any method or apparatus known to those skilled in the art, such as one or more dip tubes, one or more nozzles, ejectors, static mixing devices, and / or one or more spargers, etc. The alkene and carbon tetrachloride used in the process of the present invention can be contacted in the zone (e.g., primary alkylation zone or primary alkylation zone) by feeding the zone through a dispersion device. In such embodiments, the alkene and / or carbon tetrachloride feed can be continuous or intermittent. The alkene supplied as a feed to the zone in which the reaction mixture is formed can be in liquid and / or gaseous form. Similarly, carbon tetrachloride can be in liquid and / or gaseous form.

In an embodiment of the present invention, present in the major alkylation zone (and / or any other alkylation zone that can be used) (carbon tetrachloride, C 3 _{~ 6} chlorinated alkanes product, and optionally The reaction mixture (including the catalyst and / or unreacted alkene) can be homogeneous, ie, single phase, eg, liquid phase or gas phase. This can be achieved even if one of the components of the reaction mixture is introduced into the other components in the system in different phases. For example, in an embodiment, contacting a gaseous alkene with liquid carbon tetrachloride can dissolve the alkene, thus forming a liquid phase homogeneous reaction mixture. Alternatively, the reaction mixture can be heterogeneous.

According to one aspect of the present invention, and to produce a C _{3 ~ 6} chlorinated alkane in the reaction mixture giving a reaction mixture comprising an alkene and carbon tetrachloride in the primary alkylation zone, the reaction from the primary alkylation zone Extracting a portion of the mixture, supplying a portion of the extracted reaction mixture to the main reaction zone, and extracting a portion of the reaction mixture from the main reaction zone, from the main alkylation zone C _{3 ~ 6} chlorinated alkane of the extracted reaction mixture: four molar ratio of carbon tetrachloride is, C _{3 ~ 6} chlorinated alkane in the reaction mixture was extracted from the primary alkylation zone: higher than four molar ratio of carbon tetrachloride the method of C 3 _{~ 6} chlorinated alkanes is provided.

Alkenes used in the method of the present invention, C 2 _{~ 5} alkenes, such as ethene (i.e. C ₂ alkene), can be propene, butene or pentene. Alkenes may or may not be halogenated, for example chlorinated, and / or may or may not be substituted. In the sequence for chlorinating alkenes, it preferably contains 1, 2, 3, 4 or 5 chlorine atoms. In an embodiment of the invention, the chloroalkene has the general formula: CH _a X _b = R, wherein a is 1 or 2, b is 0 or 1, and X is a halogen (eg chlorine), R is substituted or unsubstituted C _1-4 alkyl.

  Examples of alkene materials that can be used in the process of the present invention include ethene, vinyl chloride, propene, 2-chloropropene, 3-chloropropene, 2,3,3,3-tetrachloropropene, 1,1-dichloroethane. In US Pat. No. 5,902,914 and EP 131561, the contents of which are incorporated by reference, with respect to benzene, trichloroethene, chlorofluoroethene, 1,2-dichloroethene, 1,1-dichloro-difluoroethene, 1-chloropropene, 1-chlorobutene, and / or Any of the other disclosed alkenes can be mentioned.

  The carbon tetrachloride and alkene starting materials used in the method of the present invention can have a high purity, for example, the purity of either or both of these materials is at least about 95%, at least about 97%, at least about 99%. , At least about 99.5%, at least about 99.7%, or at least about 99.9%.

  In embodiments of the invention, the carbon tetrachloride starting material is less than about 2000 ppm, less than about 1000 ppm, less than about 500 ppm, less than about 200 ppm, less than about 100 ppm, less than about 50 ppm, or less than about 20 ppm bromide or brominated organic compound. including.

  In addition or alternatively, the water content of the carbon tetrachloride starting material can be about 200 ppm or less, about 100 ppm or less, about 50 ppm or less, or about 35 ppm or less.

  In the method of the present invention, carbon tetrachloride is preferably used as a haloalkane raw material. However, in alternative embodiments of the present invention, haloalkane raw materials other than carbon tetrachloride can be used, such as 1,1-dichloromethane, 1,1,1-trichloroethane, dichlorofluoromethane, 1,1,1-trichloro. Use any of trifluoroethane, 1,1,2-trichlorotrifluoroethane, tetrachloroethane, pentachloroethane, hexachloroethane, and / or other chloroalkanes disclosed in US Pat. No. 5,902,914, the contents of which are incorporated into this disclosure. be able to.

  The source of carbon tetrachloride can be placed in the same location as the apparatus for carrying out the method of the present invention. In an embodiment, the source of carbon tetrachloride can be adjacent to a chlor-alkali facility including, for example, a membrane electrolysis plant (high purity chlorine derived therefrom can be used to produce carbon tetrachloride). The location produces epichlorohydrin (eg, from glycerol raw materials), glycidol, and / or epoxy resins so that hydrogen chloride gas produced as a by-product in any relevant process or process is also effectively used. Plants can also be included. Thus, for the most economical use of chlor-alkali facilities, a collective facility comprising a plant for chlorine reaction and hydrogen chloride collection / reuse is envisaged.

  The reaction mixture can be extracted continuously or intermittently from the primary alkylation zone (and / or primary alkylation zone, if used). For the avoidance of doubt, this should not be construed in a purely literal sense when referred to in this case for the continuous extraction of substances from the zones used in the method of the invention. Those skilled in the art will recognize that, in such embodiments, if the objective is to set up a steady state reaction (eg, alkylation) while the zone in question is an operating condition, the reaction mixture therein is brought to the required steady state. Once reached, it will be recognized that the substance can be removed substantially continuously.

  One advantage of the present invention is the disclosure of the presence of certain impurities typically observed in commercially supplied alkenes (eg, certain organic impurities such as alcohols, ethers, esters, and aldehydes). Can be adjusted and / or eliminated using the process steps outlined in. This advantage is particularly beneficial in sequences where the alkene is an ethene that can be derived from bioethanol, ethanol or crude oil.

  A further advantage of the process of the invention is that i) continuous production of chlorinated alkanes and ii) substantially complete use of the alkene starting material can be achieved without leakage of the alkene into the exhaust system. is there.

C 3 _{~ 6} chlorinated alkanes chloropropane can be chlorobutane, chloropentane, or chloro hexane. C 3 _{~ 6} chlorinated alkanes, 4, 5, 6, 7, can include eight or more chlorine atoms. Examples of C _{3 ~ 6} chlorinated alkane compounds that can be prepared in high purity according to the process of the present invention, tetrachloropropane (e.g. 1,1,1,3-tetra-chloropropane), tetrachlorobutane, hexachloro butane, Examples include heptachlorobutane, octachlorobutane, pentachloropropane, pentachlorobutane (eg, 1,1,1,3,3-pentachlorobutane), and heptachlorohexane.

One advantage of the method of the present invention is that it in some cases to permit the production of C _{3 ~ 6} chlorinated alkane of interest with high isomer selectivity. Accordingly, in an embodiment according to the present invention, a C _{3 ~ 6} chlorinated alkanes product, at least about 95%, at least about 97%, at least about 98%, at least about 99%, at least about 99.5%, at least about Produced with an isomer selectivity of 99.7%, at least about 99.8%, or at least about 99.9%.

The alkylation reaction to produce a C _{3 ~ 6} chlorinated alkanes carried out in the method of the present invention, may be facilitated by use of a catalyst. The term catalyst as used in this disclosure includes not only the use of a single compound or material having a catalytic effect, such as a solid metal or metal salt, but additionally includes catalytic materials and cocatalysts or promoters, such as ligands. Catalyst systems that can be used are also included.

It is possible to use any catalyst utilized known to those skilled in the art which have been found of the formation of C _{3 ~ 6} chlorinated alkanes from carbon tetrachloride and alkenes.

  In an embodiment of the invention, the catalyst is metallic. Any metal that can function as a catalyst in the alkylation reaction of the present invention can be used, including but not limited to copper and / or iron. The metal-based catalyst can be present in solid form (eg in the case of copper or iron, granular form (eg powder or filings), wire and / or mesh etc.) and / or in any oxidation state of the metal. Salts that can be present (eg cuprous salts such as cuprous chloride, cuprous bromide, cuprous cyanide, copper (I) sulfate, phenyl copper (I), and / or ferrous and / or Or as a ferric salt, such as ferrous chloride and ferric chloride).

  If a metal salt is used as a catalyst in the process of the present invention, it can be added to and / or formed in situ in one or more alkylation zones. In the latter case, the solid metal can be added to one or more alkylation zones, and the conditions therein may form a salt. For example, when solid iron is added to the chlorination reaction mixture, the chlorine present can combine with elemental iron to form ferric chloride or ferrous chloride in situ. Maintains a predetermined concentration of elemental metal catalyst in the reaction mixture (eg, one or more metal salts and / or excess elemental metal compared to the ligand concentration) when the metal salt is formed in situ Although it may be desirable to do so, additional elemental metal catalysts can therefore be added to allow the reaction to proceed continuously or intermittently.

  As mentioned above, in embodiments of the present invention, the catalyst can also include a ligand, preferably an organic ligand capable of complexing with a metal-based catalyst. Suitable ligands include amines, nitrites, amides, phosphates, and phosphites. In an embodiment of the invention, the ligand used is an alkyl phosphate such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, and triphenyl phosphate.

  Additional metal-based catalysts and ligands are known to those skilled in the art and are disclosed in the art, eg, US Pat. No. 6,187,978, the contents of which are incorporated by reference.

  Feeding the components of the catalyst system continuously or intermittently, if used, to one or more alkylation zones (eg, primary alkylation zone and / or primary alkylation zone, if used) Can do. In addition or alternatively, it may be added to one or more alkylation zones (eg, primary alkylation zone, and / or primary alkylation zone, if used) before the initiation of the alkylation reaction and / or It can be introduced during the start of the conversion reaction.

  Additionally or alternatively, the catalyst (or catalyst component, eg, ligand) is added to one or more alkylation zones (eg, primary alkylation zone, or primary alkylation zone, if used) of the reaction mixture. For example in a carbon tetrachloride and / or ethene feed.

  In embodiments of the invention in which the catalyst comprises a metal-based catalyst and a promoter such as a ligand, the promoter in the main alkylation zone and / or reaction mixture present in the primary alkylation zone, if used: metal The molar ratio of the system catalyst is maintained at a ratio greater than 1: 1, more preferably greater than 2: 1, 5: 1, or 10: 1.

  If a solid metal catalyst is added to the reaction mixture, it can be added to the primary alkylation zone and / or the main alkylation zone, if used. In embodiments of the present invention, solid metal catalyst, if used, is about 0.1-4%, about 0.5-3% by weight of the reaction mixture in the primary alkylation zone and / or main alkylation zone, Or added in an amount to maintain a concentration of about 1-2% by weight.

  In addition or alternatively, if a metal-based catalyst is used, it is about 0.1%, about 0.15% or about 0.2% to about 1.0%, about 0.00% by weight of the reaction mixture. Add to establish a dissolved metal content of 5% by weight or about 0.3% by weight.

  In an embodiment of the invention in which the catalyst system used comprises a metal catalyst and a promoter, the metal catalyst and promoter can be added simultaneously to the reaction mixture and / or the same part of the apparatus, for example (if used) ) It can be added in the primary alkylation zone and / or in the main alkylation zone.

  Alternatively, the metal-based catalyst and promoter can be added sequentially or separately at different locations in the apparatus. For example, the solid metal catalyst can be added to the primary alkylation zone along with the promoter supplied to the zone from a recycle loop where additional unused promoter can also be added.

  In an embodiment of the present invention, the primary and / or primary alkylation zone is at or below ambient pressure, ie greater than about 100 kPa, greater than about 200 kPa, greater than about 300 kPa, greater than about 400 kPa, greater than about 500 kPa, greater than about 600 kPa. Operating at a pressure above about 700 kPa, or above about 800 kPa. Typically, the pressure in the primary and / or primary alkylation zone is about 2000 kPa, about 1700 kPa, about 1500 kPa, about 1300 kPa, about 1200 kPa, or about 1000 kPa or less.

  In addition or alternatively, in embodiments of the present invention, the primary and / or primary alkylation zones may be heated to an elevated temperature, i. It is operated at a temperature of about 90 ° C. or about 100 ° C. or higher. Typically, the primary and / or primary alkylation zone is operated at a temperature of about 200 ° C, about 180 ° C, about 160 ° C, about 140 ° C, about 130 ° C, about 120 ° C, or about 115 ° C.

Use of temperature and pressure within these ranges in combination with other features of the method of the present invention, while minimizing the formation of by-products in question, of C _{3 ~ 6} chlorinated alkanes object yields and / Or it has been found to be advantageous to maximize selectivity.

  Multiple alkylation zones can be used in the process of the present invention. Any number of alkylation zones can be used, for example 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 or more. In embodiments using multiple primary and / or primary alkylation zones, any number (eg, one, two, three, four, five, six, seven, eight, nine, or ten) There may be one or more primary and / or primary alkylation zones.

  To avoid misunderstandings, when referring to characteristics of the alkylation zone (primary and / or primary), such as operating conditions, method of operation, characteristics, etc., embodiments of the present invention may include multiple primary and / or primary alkylations. As far as including zones, one, some, or all of these zones can exhibit one or more characteristics in question. For example, for the sake of brevity, when referring to a primary alkylation zone having a particular operating temperature, as far as embodiments involving multiple primary alkylation zones are concerned, this is one of the primary alkylation zones, Some or all should be taken as a reference to operate at that particular temperature.

  In arrangements using multiple primary and / or primary alkylation zones, the alkylation zones can operate in parallel or in series.

In arrangements using primary and primary alkylation zones, the alkylation reaction between alkene and carbon tetrachloride can be controlled to prevent it from progressing beyond a certain degree of completion in the primary alkylation zone, for example , it is extracted from the primary alkylation zone, and / or C _{3 ~ 6} chlorinated alkane in the reaction mixture fed to the main alkylation zone: four molar ratio of carbon tetrachloride are, although not essential 85: 15, 90: 10, 93: 7, or 95: 5 may not be exceeded. Additionally or alternatively, the primary alkylation zone is extracted from, and / or C _{3 ~ 6} chlorinated alkane in the reaction mixture fed to the main alkylation zone: four molar ratio of chloride carbon, 50: 50, The reaction can be allowed to run to a relatively advanced stage of completion, such as exceeding 60:40, 70:30, 75:25, or 80:20.

  Control of the progress of the alkylation reaction in the primary alkylation zone can be achieved by the use of reaction conditions that are not favorable for the total conversion of carbon tetrachloride to 1,1,1,3-tetrachloropropane. In addition or alternatively, the control of the progress of the alkylation reaction in the primary alkylation zone can be controlled by careful selection of the residence time of the reaction mixture in the primary alkylation zone, such as about 20-300 minutes, about 40-250 minutes, It can be achieved in about 60 to about 200 minutes, or about 90 to about 180 minutes. In embodiments of the invention, the molar ratio can be controlled by limiting the amount of alkene fed to the primary and / or primary alkylation zone. For example, the molar ratio of carbon tetrachloride: alkene fed to the primary and / or primary alkylation zone is about 50:50 to about 55:45, about 60:40, about 65:35, about 70:30, about It can be in the range of 75:25, about 80:20, about 85:15, or about 90:10.

In embodiments using a primary and primary alkylation zone, it is possible to manufacture the most C 3 _{~ 6} chlorinated alkanes at the primary alkylation zone. In such embodiment, the proportion of C _{3 ~ 6} alkane produced in the primary reaction zone, for example the reaction mixture C _{3 ~ 6} chlorinated alkanes in: four molar ratio of carbon tetrachloride from 1 to 10, 2 8, Or it can be low enough to increase by 3 to 5.

For example, extracted from the primary alkylation zone, C _{3 ~ 6} chlorinated alkane in the reaction mixture fed to the main alkylation zone: four case the molar ratio of carbon tetrachloride is 90:10, extracted from the main alkylation zone C _{3 ~ 6} chlorinated alkanes present in the mixture that is: four molar ratio of carbon tetrachloride is 92: 8,93: 7, or 95: as can be 5, the molar ratio in the main alkylation zone It can be increased by 2, 3, or 5.

However, feasibility of the method of the present invention does not depend on the bulk of the conversion of carbon tetrachloride to the desired C _{3 ~ 6} chlorinated alkanes which occurs in the primary reaction zone. Accordingly, in an alternative embodiment, the degree of fourth carbon tetrachloride conversion to C _{3 ~ 6} chlorinated alkanes of interest, can be balanced between the primary and major alkylation zone, or major than the primary alkylation zone alkyl It may be large in the conversion zone.

Thus, the reaction mixture from the primary alkylation zone (continuously or intermittently) removed some of the carbon tetrachloride remaining present in the reaction mixture, to conversion to C _{3 ~ 6} chlorinated alkane of interest It can be fed to the main alkylation zone. In such embodiments, any unreacted alkene starting material present in the reaction mixture can advantageously be used completely (or at least almost completely).

  When used in the process of the present invention, the primary and primary alkylation zones can be operated under different conditions. The primary alkylation zone is at a higher pressure than the one or more primary alkylation zones, e.g., at least about 10 kPa higher, about 20 kPa higher, about 50 kPa higher, about 100 kPa higher, about 150 kPa higher, about 200 kPa higher, about 300 kPa or about 500 kPa. Can operate under high pressure.

  In embodiments of the present invention, the alkene may not be fed to the main alkylation zone, and the only source of alkene for that zone or zones is in the reaction mixture fed to the main alkylation zone. it can.

  In addition, in embodiments where the alkylation reaction between carbon tetrachloride and alkene is catalyzed by a metal-based catalyst (optionally including a ligand), the metal-based catalyst and / or ligand is not fed to the main alkylation zone. It's okay. In such embodiments, the only source of catalyst can be the reaction mixture fed to the main alkylation zone. In addition or alternatively, a catalyst bed can be provided in the main alkylation zone.

  In order to feed the primary alkylation zone in the process of the present invention, using the primary and primary alkylation zones, the solid metal catalyst is present in the reaction mixture in the primary alkylation zone (eg by adding directly thereto). In addition, when extracting the reaction mixture from the primary alkylation zone, the extraction of the reaction mixture from the primary alkylation zone may involve very little (if any) solid metal catalyst (eg, less than about 5 mg per liter of reaction mixture, about 2 mg). Less than about 1 mg, less than about 0.5 mg, less than about 0.2 mg, less than about 0.1 mg solid metal catalyst) may be present in the reaction mixture.

  This comprises any method and / or apparatus known to the person skilled in the art, for example a filter mesh and / or has a suitable diameter and extends to one or more primary alkylation zones at suitable locations. Can be achieved by the use of a tube.

  If used, the primary and primary alkylation zones can be in the same or different reactors, which can be the same or different types of reactors. Further, in embodiments using multiple primary alkylation zones, these can be in the same or different reactors. Similarly, in embodiments using multiple primary alkylation zones, these can be in the same or different reactors.

  Any type of reactor or reactor known to those skilled in the art can be used in the process of the present invention. Specific examples of reactors that can be used to provide an alkylation zone include column reactors (eg, column gas-liquid reactors), tubular reactors, bubble column reactions, plug / flow reactors (eg, tubular plug / flow reactors). Flow reactors) and stirred tank reactors (eg, continuous stirred tank reactors).

  An arrangement in which the primary alkylation zone was in a continuous stirred tank reactor (CSTR) and the primary alkylation zone was in a plug / flow reactor gave advantageous results.

  One advantage of the method of the present invention is desired regardless of whether the alkylation zone (eg, primary alkylation zone and / or primary alkylation zone) operates in a continuous (steady state) process or a batch process. The result is to be obtained. The terms “continuous process” and “batch process” will be understood by those skilled in the art.

  In embodiments, when used, the primary alkylation zone is operated in a continuous or batch process. In addition or alternatively, when used, the second one or more alkylation zones are operated in a continuous or batch process.

In the method of the present invention, the concentration of C _{3 ~ 6} chlorinated alkane in the reaction mixture in the primary alkylation zone, C _{3 ~ 6} chlorinated alkane in the reaction mixture extracted from the primary alkylation zone: carbon tetrachloride At a concentration such that the molar ratio does not exceed i) 95: 5 (when the primary alkylation zone is in continuous operation) or ii) 99: 1 (when the primary alkylation zone is in batch operation) maintain.

In certain embodiments of the present invention that the primary alkylation zone is in continuous operation, C 3 _~ content of ₆ chlorinated alkanes, the compound of the extracted from the main alkylation zone reaction mixture: four ratio chloride carbon , About 94: 6, about 92: 8, or about 90:10.

In an alternative embodiment of the present invention that the primary alkylation zone is batchwise operation, C 3 _~ content of ₆ chlorinated alkanes, the compound in the reaction mixture extracted from the primary alkylation zone: carbon tetrachloride The ratio can be controlled to not exceed about 97: 3, about 95: 5, or about 90:10.

Regardless major or alkylation zone is either batchwise process is a continuous process, C 3 _~ content of ₆ chlorinated alkanes, the compound in the reaction mixture extracted from the primary alkylation zone: carbon tetrachloride The ratio of about 70:30, about 80:20, about 85:15, or about 90:10 or more.

Surprisingly, by controlling the extent of conversion to the desired C _{3 ~ 6} chlorinated alkane carbon tetrachloride, and by preventing the reaction proceeds to completion, the formation of impurities is advantageously reduced It was found that For example, in embodiments where the alkene feed used in the process of the present invention is ethene, the formation of undesirable by-products such as pentane (otherwise formed) is minimized.

Accordingly, in an embodiment of the present invention, the reaction mixture was extracted from the main reaction zone, a series of reaction products, i.e. C _{3 ~} less large carbon number compounds than ₆ chlorinated alkane product about 5%, about 2 %, Less than about 1%, less than about 0.5%, less than about 0.2%, less than about 0.1%, less than about 0.05%, or less than about 0.02%.

The control of the content of C 3 _{~ 6} chlorinated alkanes, to slow the progression of the alkylation process, and / or additional carbon tetrachloride can be achieved by introducing into the primary alkylation zone.

C 3 In the embodiment controlled by delaying the _1-6 chlorination alkylation process the content of alkanes, which are the reaction conditions do not favor the total conversion of fourth carbon tetrachloride 1,1,1,3 tetrachloropropane Can be achieved through the use of For example, this can be accomplished by subjecting the reaction mixture or at least a portion thereof to conditions that slow or stop the progress of the alkylation reaction. In such embodiments, the pressure experienced by the reaction mixture in one or more alkylation zones (eg, one or more primary alkylation zones, if used) is sufficient, eg, at least about 500 kPa, at least about 700 kPa, It can be reduced by at least about 1000 kPa.

  Additionally or alternatively, the pressure experienced by the reaction mixture can be reduced to ambient pressure or a pressure below ambient pressure. The pressure reduction can occur in one or more alkylation zones (eg, one, some, or all of the primary alkylation zones, if used). In addition or alternatively, pressure reduction can occur following extraction of the reaction mixture from one or more alkylation zones.

Additionally or alternatively, in embodiments be controlled by delaying the alkylation process the content of C 3 _{~ 6} chlorinated alkanes, which may be achieved by limiting the alkene concentration present in the reaction mixture Can do.

  In an embodiment of the present invention, the control of the progress of the alkylation reaction in one or more alkylation zones can be achieved by careful selection of the residence time of the reaction mixture in one or more alkylation zones. it can. For example, in embodiments using one or more primary alkylation zones, the residence time of the reaction mixture in one or more of the zones is, for example, about 1 to 120 minutes, about 5 to 100 minutes, about 15 Can be from about 60 minutes, or from about 20 to about 40 minutes.

In the embodiment controlled by delaying the alkylation process the content of C 3 _{~ 6} chlorinated alkanes, this is, in addition, or alternatively, be achieved by lowering the operating temperature of the primary alkylation zone (Eg, about 5 ° C. or higher, about 10 ° C. or higher, about 20 ° C. or higher, about 50 ° C. or higher, or about 100 ° C. or higher). In addition or alternatively, the operating temperature of the main conversion zone can be reduced to about 20 ° C, about 10 ° C, or about 0 ° C.

  In addition or alternatively, the alkylation process can be delayed by limiting the amount of catalyst present in the reaction mixture or by removing the catalyst bed (if present) from the main alkylation zone. .

  It is also possible to slow down the alkylation process by reducing the speed of agitation or stirring of the main alkylation zone.

As mentioned above, the reaction mixture was extracted from the main alkylation zone includes a carbon tetrachloride and C _{3 ~ 6} chlorinated alkanes. However, in embodiments of the present invention, depending on the conditions and equipment used, the reaction mixture extracted from the main alkylation zone may contain unreacted alkene starting materials, catalysts, and / or impurities (eg, chlorinated alkane impurities). , Chlorinated alkene impurities, and / or oxygenated organic compounds).

The presence unreacted alkene with C 3 _{~ 6} chlorinated alkanes, particularly, if there can be a problem with downstream processes using the C 3 _{~ 6} chlorinated alkanes, in embodiments of the present invention, the main Reaction wherein the reaction mixture extracted from the alkylation zone is extracted from at least about 50% by weight or more of the alkene present in the reaction mixture and at least about 50% of the extracted alkene is provided in the main alkylation zone It is subjected to a dealkenylation step that returns to the mixture.

  Such an embodiment is particularly advantageous since it is substantially possible if not fully used of the alkene feed used in the process of the present invention.

  In embodiments of the invention, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, at least about at least about alkene present in the reaction mixture extracted from the main alkylation zone. 97%, or at least about 99% is removed during the dealkenylation step.

  Removal of unreacted alkene from the reaction mixture can be accomplished using any method known to those skilled in the art. In an embodiment of the present invention, the extraction of the alkene from the reaction mixture may be accomplished by distillation methods that result in a stream enriched in the resulting alkene, such as ethene (−103.7 ° C.) versus carbon tetrachloride (76.6 ° C.) and 1 Flash, which can be conveniently arranged in embodiments where the boiling point of the alkene is sufficiently lower than the boiling point of other compounds present in the reaction mixture, such as 1,1,1,3-tetrachloropropane (159 ° C.) It can be achieved using distillation.

  Dealkenylation of the reaction mixture can be selective. In other words, the alkene is selectively extracted without sufficient removal of other compounds from the reaction mixture. In such embodiments, the alkene extracted from the reaction mixture can comprise less than about 10%, less than about 5%, less than about 2%, or less than about 1% of a compound other than the alkene starting material.

  Distillation of the reaction mixture can be accomplished by any method or any apparatus known in the art. For example, a conventional distillation apparatus (for example, a distillation column) can be used. In addition or alternatively, in embodiments of the present invention, if the pressure in the main alkylation zone from which the reaction mixture is extracted is lower than the ambient pressure, the evaporation of the alkene from the reaction mixture will result in extraction from the main alkylation zone. Can be achieved by maintaining the reaction mixture at a pressure below the ambient pressure after and supplying it to the evaporation zone where evaporation of the alkene from the reaction mixture takes place.

In an embodiment of the present invention, the evaporation of the alkene from the reaction mixture in the evaporation zone is a depressurization, such as a pressure at which the reaction mixture is at least about 500 kPa, at least about 700 kPa, at least about 1000 kPa lower, and / or ambient pressure or This can be achieved by sufficiently reducing the pressure below the ambient pressure. Advantageously, implementation depressurization partially or totally used to slow the conversion of carbon tetrachloride to C _{3 ~ 6} chlorinated alkanes of interest, or is stopped, further to separate the alkene from the reaction mixture In embodiments, these objectives can be achieved simultaneously in one depressurization step.

  The evaporation zone can be any device capable of achieving evaporation of the alkene present in the reaction mixture, for example a flash evaporation device such as a flash drum.

  The alkene distilled from the reaction mixture, for example by flash evaporation, is extracted from the distillation apparatus, preferably in liquid or gaseous form.

  In the method of the present invention, at least about 50%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, at least about 97% by weight of the alkene extracted from the evaporation zone, Or at least about 99% by weight is returned (ie, recycled) to the primary and / or main alkylation zone.

  To avoid misunderstandings, in embodiments of the present invention, the distilled alkene, if in gaseous form, may be returned to liquid before being fed to the reaction mixture fed to the main alkylation zone, or There is no need to return it. For example, the conversion of a gaseous alkene to a liquid alkene can be accomplished by passing through a condenser and / or collecting in a liquid (preferably cooled) carbon tetrachloride stream, It can then be fed to one or more alkylation zones. Gaseous alkenes can be collected in a liquid stream of carbon tetrachloride using any method or apparatus known to those skilled in the art, such as an absorption column. This arrangement is advantageous for the purpose of maximal industrial utilization of the compounds used in the alkylation process.

As mentioned above, in embodiments of the present invention, a reaction comprising a catalyst system comprising a catalyst, such as a solid metal and / or metal salt catalyst, and a promoter such as a ligand, is present in one or more alkylation zones. It can be used in a mixture. In such embodiments, the reaction mixture extracted from one or more alkylation zones can include a catalyst. The presence of the catalyst, if there can be a problem in the downstream reaction using C 3 _{~ 6} chlorinated alkanes, it may be preferable to remove the catalyst from the reaction mixture.

  In addition, with respect to catalyst systems using high cost catalysts and / or promoters, such as the alkyl phosphates and alkyl phosphite ligands referred to above, reusable catalyst systems and / or recovery of their components must be used. This is preferred because it minimizes the amount of unused catalyst that must be run, thus reducing operating costs.

  While attempts have been made previously to remove the type of catalyst used in the process of the invention from the reaction mixture, the process and conditions used to do so (including typically distillation using harsh conditions) Can damage the catalyst system and reduce its catalytic performance. This is especially the case when the catalyst system is temperature sensitive, as in the case of systems containing certain organic ligands such as alkyl phosphates and alkyl phosphites as promoters.

  Thus, in an embodiment of the present invention, the reaction mixture extracted from the main alkylation zone is contacted with an aqueous medium in the aqueous treatment zone to form a biphasic mixture and the organic phase containing the catalyst is biphasic. Subjected to an aqueous treatment step extracted from the mixture.

In an embodiment of the present invention subjecting the reaction mixture to an aqueous process, the reaction mixture can include a carbon tetrachloride and C _{3 ~ 6} chlorinated alkane product unreacted. In addition, the reaction mixture can include a catalyst (eg, a complex of a metal-based catalyst and a catalyst ligand, or a free catalyst ligand) and / or unreacted alkene starting material.

  The use of an aqueous treatment step can avoid the damage conditions described in the prior art (eg high temperature, high catalyst concentration, and / or the presence of iron compounds in anhydrous form), which can be achieved with recovered catalyst and / or Or that component (eg, ligand or promoter) can be reused (eg, it can be returned to the reaction mixture fed to one or more alkylation zones) without significant loss of catalyst performance. In an embodiment of the present invention, steam stripping of the biphasic aqueous treated mixture is preferred because it can avoid boiler temperatures above 100 ° C. and environmental pressures can be used.

  A further advantage of the aqueous processing step is that it results in the removal of impurities from the reaction mixture, such as oxygenated organic products, if present. More specifically, the process includes as precursors alkenes such as ethene, propene, 1-butene, 2-butene, 1-hexene, 3-hexene, 1-phenyl-3-hexene, butadiene, vinyl halide, etc. In some cases, there is the potential to form oxygenated organic compounds such as alkanols, alkanoyls, and chlorinated derivatives of such oxygenated compounds. Advantageously, the concentration of such substances in the reaction mixture is sufficiently reduced to an acceptable concentration, even if it does not disappear by an aqueous treatment step.

In an embodiment of the present invention to carry out the aqueous treatment step, the reaction mixture given in the aqueous treatment zone, (for example an amount of more than about 50%) C _{3 ~ 6} chlorinated alkanes of interest, the catalyst, and optionally It may include carbon tetrachloride and / or impurities, such as organic oxygenated compound, (C _{3 ~} other than _six chlorinated alkane of interest) chlorinated alkane compounds, and or chlorinated alkene compound.

  This catalyst recovery process involves subjecting the reaction mixture to an aqueous treatment step in which the reaction mixture is contacted with an aqueous medium in an aqueous treatment zone. In an embodiment, the aqueous medium is water (as liquid and / or vapor). In addition, the aqueous medium can additionally contain other compounds, for example acids. Inorganic acids such as hydrochloric acid, sulfuric acid, and / or phosphoric acid can be used.

  If the aqueous medium fed to the aqueous treatment zone is partially or wholly in liquid form, a biphasic mixture forms when the liquid aqueous medium comes into contact with the reaction mixture.

  Alternatively, if the aqueous medium is in a gaseous form, such as steam, the biphasic mixture may not immediately form and once the gaseous aqueous medium condenses. The equipment used in the aqueous treatment process can be configured such that condensation of the aqueous medium that forms the biphasic mixture occurs within and / or away from the aqueous treatment zone.

In an embodiment of the present invention, a C 3 _{~ 6} chlorinated alkanes product can be extracted from the mixture formed in an aqueous treatment zone. Most (e.g., at least about 50% of C _{3 ~ 6} chlorinated alkanes present in the reaction mixture fed to the aqueous treatment zones, at least about 60%, at least about 70%, at least about 80%, or at least about 90% ) Can be extracted from the mixture formed in the aqueous treatment zone using any method or apparatus known to those skilled in the art.

In an embodiment of the present invention, using distilled to extract the C _{3 ~ 6} chlorinated alkane product from the mixture formed in an aqueous treatment zone. Distillation can result in rich stream obtained C _{3 ~ 6} chlorinated alkanes product.

  As used throughout this specification, the term "rich stream" of a particular compound (or corresponding term) is at least about 90%, about 95%, about 97%, about 98%, or about 99% of the stream. Are used to mean including the following specific compounds: Furthermore, the term “stream” should not be construed narrowly, but encompasses compositions (including fractions) extracted from the mixture via any method.

For example, it is possible to distill the C 3 _{~ 6} alkanes from gaseous mixture comprising the alkane and steam. The C 3 _{~ 6} chlorinated alkanes can be distilled in a rich stream C 3 _{~ 6} chlorinated alkanes. Aqueous medium, in an embodiment of the partially or wholly present invention which is in liquid form, the distillation of C 3 _{~ 6} chlorinated alkanes, was boiled present mixture is evaporated C _{3 ~ 6} chlorinated alkanes can be achieved by preparing gaseous C _{3 ~ 6} chlorinated alkane / water vapor mixture (which can be distilled using, for example a steam distillation method now C _{3 ~ 6} chlorinated alkanes).

Additionally or alternatively, when giving the aqueous medium partially or totally in the gaseous form, which, by evaporating the C 3 _{~ 6} chlorinated alkanes to form a gaseous mixture comprising an alkane and steam , it is then optionally distilled, for example, subjected to a steam distillation can remove the C 3 _{~ 6} chlorinated alkanes. The C 3 _{~ 6} chlorinated alkanes may be obtained rich stream of the compound.

C 3 In the embodiment of distilling _{~ 6} chlorinated alkanes from gaseous mixtures C _{3 - 6} chlorinated alkanes and water vapor, the gaseous chlorinated alkane / water vapor mixture is directly passed to a distillation apparatus from the aqueous treatment zone Can be coupled to the aqueous treatment zone. Alternatively, the distillation apparatus can be located away from the aqueous treatment zone so that the gaseous mixture is first extracted from the aqueous treatment zone and then transported to the distillation apparatus. In either arrangement, the C 3 _{~ 6} chlorinated alkanes may be obtained rich stream of the compound.

In an alternative embodiment, it is the case the aqueous medium and the reaction mixture is in liquid form, by using the conventional distillation methods known to those skilled in the art, to extract the C 3 _{~ 6} chlorinated alkanes from the liquid mixture it can. The C 3 _{~ 6} chlorinated alkanes may be obtained rich stream of the compound.

The biphasic mixture can be formed in or away from the aqueous treatment zone. Biphasic mixture (as a result of the addition of an aqueous medium in the aqueous treatment zone) aqueous phase, and (C 3 _{~ 6} chlorinated alkanes, optionally unreacted carbon tetrachloride, and importantly catalyst Organic phase).

In order to maximize the volume of the organic phase and thus facilitate the extraction of that phase from the biphasic mixture, haloalkane extractants (eg carbon tetrachloride, and / or or object C _{3 ~ 6} chlorinated alkanes) of by continuously or intermittently supplied to the biphasic mixture (e.g. aqueous treatment zones) can be added.

  The organic phase can be extracted from the biphasic residue using any method known to those skilled in the art, such as decantation. For example, extraction of the organic phase can be performed by sequential phase extraction from the aqueous processing zone or vessel containing it. Alternatively, the biphasic mixture can be extracted from the aqueous treatment zone and subjected to a phase separation step away from the aqueous treatment zone.

  In an embodiment of the invention, the biphasic mixture and / or the extracted organic phase can be filtered. In embodiments, this results in the resulting filter cake that can optionally be used in whole or in part as a source of iron.

Extraction of C _{3 ~ 6} chlorinated alkane product from the mixture formed in the aqueous treatment step, prior to the extraction of the organic phase therefrom, and / or be carried out after extracting the organic phase from the mixture it can. Some exemplary embodiments of extracting C _{3 ~ 6} chlorinated alkane product from the mixture formed in an aqueous process, outlined above.

As a further example, biphasic mixture was heated to can form a gaseous mixture, from which via a C _{3 ~ 6} chlorinated alkane product for example by distillation (optionally C _{3 ~ 6} chlorination Can be extracted as a stream rich in alkanes). Then the organic phase having a reduced proportion of C 3 _{~ 6} chlorinated alkanes can be extracted from the biphasic mixture.

In addition or alternatively, the organic phase can be extracted from the biphasic mixture as discussed above. The C 3 _{~ 6} chlorinated alkanes, followed by (a rich stream optionally C _{3 ~ 6} chlorinated alkanes) from the phases via, for example, distillation can be extracted. In such embodiment, when the organic phase comprises a catalyst, selected distillation conditions to extract C 3 _{~ 6} chlorinated alkanes are mild to minimize deactivation of the catalyst system (e.g., about 100 ° C or lower, about 95 ° C or lower, about 90 ° C or lower, about 85 ° C or lower, or about 80 ° C or lower, and / or a pressure of about 1 to 10 kPa). In addition, or alternatively, lower pressures can be used.

The extracted organic phase can include carbon tetrachloride, and / or C _{3 ~ 6} chlorinated alkanes product. In addition, the reaction mixture can include a catalyst (eg, a metal-based catalyst and a catalyst ligand complex, or a ligand-free complex) and / or unreacted alkene starting material. C 3 _~ rich stream ₆ chlorinated alkane mixture formed in an aqueous process (directly or after extraction of the organic phase therefrom) When extracted, C _{3 ~ 6} chlorine that phase The alkane fluoride content will be lower than in the reaction mixture.

  In the arrangement according to the invention, in particular those in which the organic phase comprises carbon tetrachloride and / or a catalyst, the organic phase can be returned to one or more alkylation zones, for example in liquid form. In such an arrangement, the alkene starting material (eg in gaseous form) can be collected in an organic phase stream fed to one or more alkylation zones.

  In an embodiment of the present invention, one or more distillation steps in addition to those discussed above are optionally processed to obtain one or more streams rich in a particular product. It can be implemented at any point. For example, if performed prior to the aqueous treatment step, the reaction mixture can be subjected to a distillation step. In embodiments where the reaction mixture includes a temperature sensitive catalyst system, such as one containing an organic ligand as a promoter, the distillation step is typically performed under conditions that avoid deactivation of the catalyst (eg, about 100 ° C. or less). About 95 ° C. or less, about 90 ° C. or less, about 85 ° C. or less, or about 80 ° C. or less, and / or a pressure of about 1 to 10 kPa). In addition, or alternatively, lower pressures can be used.

  In addition, it has been found that inactivation of the temperature sensitive catalyst system can be avoided by not overdistilling the reaction mixture. Thus, in an embodiment of the invention for distilling a reaction mixture containing a catalyst system, the volume of the process liquid in the distillation apparatus is reduced and the concentration of the catalyst system in the process liquid is given to the main alkylation zone. It may not be acceptable to be about 2X, about 5X, or about 10X higher than the concentration of the catalyst system present in the reaction mixture.

The distillation step carried out before the aqueous treatment step (if carried out) is carried out using techniques and equipment known to those skilled in the art, for example a distillation boiler (batch or continuous) in communication with a vacuum distillation column. can do. In such embodiment, the reaction mixture is subjected to distillation, about 50 weight percent object C _{3 ~ 6} chlorinated alkanes, catalyst, and optionally carbon tetrachloride, and / or impurities, such as organic oxygenated compounds, can contain (other than C _{3 ~ 6} chlorinated alkane of interest) chlorinated alkane compounds, and or chlorinated alkene compound.

Distillation step typically one or more chlorinated alkanes distillate stream from the reaction mixture, for example, unreacted carbon tetrachloride, (rich in optionally in) C _{3 ~ 6} alkanes of interest , and / or chlorinated organic impurities (i.e. C _{3 ~ 6} alkanes and quaternary chlorinated organic compounds other than carbon tetrachloride object) result in one or removal of a plurality of streams of. Carbon tetrachloride can be returned to one or more alkylation zones. According steps residue (typically C _{3 ~ 6} chlorinated alkanes, carbon tetrachloride, and / or an amount of the catalyst) further processing steps, for example aqueous treatment step, and / or one or more additional Can be subjected to a distillation step.

In embodiments of the invention in which the reaction mixture is subjected to a distillation step prior to the aqueous treatment step (if any), at least about 30%, at least about 50%, at least about 60%, or at least about 70%. up to about 95% by mass%, up to about 90 wt%, is removed from a maximum at about 85 weight percent, or up to the reaction mixture in its distillation process a C _{3 ~ 6} chlorinated alkanes object of about 80 wt% .

One or more distillation steps may be performed after, in addition to, or instead of the aqueous treatment step (if performed). For example, C _{3 ~ 6} chlorinated alkanes extracted from the reaction mixture fed to the aqueous treatment zone, C _{3 ~ 6} chlorinated alkanes main component, haloalkanes extractant, and chlorinated organic impurities (i.e. object C ₃ of _{~ 6} alkanes and chlorinated organic compounds other than carbon tetrachloride). The mixture was subjected to one or more distillation steps to remove the chlorinated organic impurities can get rich stream C _{3 ~ 6} chlorinated alkanes, and / or removing the haloalkane extractant Can do. Equipment or conditions known to those skilled in the art can also be used in such distillation steps, for example in a distillation boiler (batch or continuous) in communication with a vacuum distillation column.

In the distillation step according, subjecting the C _{3 ~ 6} chlorinated alkanes extracted from the reaction mixture given in the aqueous treatment zone to the distillation, it can be separated C _{3 ~ 6} chlorinated alkane of interest from chloroalkanes impurities . For example, in embodiments where C _{3 ~ 6} chlorinated alkanes 1,1,1,3 tetrachloropropane purposes, purified C _{3 ~ 6} chlorinated alkanes extracted from the reaction mixture given in the aqueous treatment zone It has been found that this distillation step is particularly effective in removing chloropentane / chloropentene impurities.

In the distillation step carried out at any stage during the process of the present invention, the chlorinated organic impurities are separated from the mixture containing the C _{3 ~ 6} chlorinated alkane of interest is recovered and reused in the production of carbon tetrachloride be able to. This can be achieved by subjecting the chlorinated organic impurities to a high temperature chlorination cracking process. In such a process, any chlorinated organic compounds present are reprocessed back mainly to high yields of pure tetrachloromethane. Thus, the use of a chlorinolysis step in the process of the present invention is useful for maximizing the overall synthesis yield and purity of the desired chloroalkane while minimizing waste products.

Regardless identity of C _{3 ~ 6} chlorinated alkanes of interest, in embodiments of the present invention can be formed in the "heavy" residue in the distillation boiler (if used subsequently to an aqueous process). “Heavy” residues are typically extracted from the system and processed (eg, preferably a high temperature chlorinolysis process that results in the production of chloromethane).

  The method of the present invention is particularly advantageous because it allows the production of high purity chlorinated alkanes using simple and straightforward techniques and equipment familiar to those skilled in the art.

  As can be appreciated from the disclosure provided in this disclosure, the method of the present invention can operate in an integrated process in a completely continuous fashion, optionally in combination with other processes. The process steps of the present invention can use starting compounds that are converted to high purity intermediates that are further processed to the required target chlorinated compounds. This compound has the purity required to be used as a raw material in the range of downstream processes, such as hydrofluoric treatment conversion.

  The process according to the invention makes it possible to control the level of purity of the product to achieve a high purity level of the compound in each step. The method advantageously reconciles particularly difficult high yields, high selectivities and high efficiencies, especially in continuous processes. The process according to the invention makes it possible to economically produce high-purity chloroalkane compounds on an industrial scale, which compounds contain very low concentrations of impurities, such as haloalkanes, or haloalkenes (especially isomers and / or compounds of interest). Or having a higher molecular weight such as products of series reactions), and / or oxygenated and / or brominated derivatives, and water, and metal species.

In an embodiment of the present invention, the method of the present invention can be used to produce a high purity chlorinated alkane composition, which is about 99.0% or more, about 99.5% or more, about 99.7% or more. About 99.8% or more, or about 99.9% or more of chlorinated alkanes,
Less than about 2000 ppm, less than about 1000 ppm, less than about 500 ppm, less than about 200 ppm, or about 100ppm less chlorinated alkane impurities (i.e., C _{3 ~} chlorinated alkane compounds other than ₆ chlorinated alkane of interest),
Less than about 2000 ppm, less than about 1000 ppm, less than about 500 ppm, less than about 200 ppm, or less than about 100 ppm, chlorinated alkene compound,
Less than about 2000 ppm, less than about 1000 ppm, less than about 500 ppm, less than about 200 ppm, or less than about 100 ppm oxygenated organic compound,
Less than about 500 ppm, less than about 200 ppm, less than about 100 ppm, less than about 50 ppm, or less than about 20 ppm of a metal-based catalyst;
Less than about 500 ppm, less than about 200 ppm, less than about 100 ppm, less than about 50 ppm, or less than about 20 ppm catalyst promoter;
Less than about 2000 ppm, less than about 1000 ppm, less than about 500 ppm, less than about 200 ppm, or less than about 100 ppm bromide or brominated organic compound, and / or less than about 1000 ppm, less than about 500 ppm, less than about 200 ppm, less than about 100 ppm, about 50 ppm Less than or less than about 20 ppm water.

In an embodiment C _{3 ~ 6} chlorinated alkanes of interest is a 1,1,1,3-tetra-chloropropane, less is minimized in the process of the present invention, not generated, and / or specific to be removed Examples of impurities are: trichloromethane, 1,2-dichloroethane, 1-chlorobutane, 1,1,1-trichloropropane, tetrachloroethane, 1,1,3-trichloropropane-1-ene, 1,1,1, 3,3-pentachloropropane, 1,1,1,2,3-pentachloropropane, hexachloroethane, 1,1,1,5-tetrachloropentane, 1,3,3,5-tetrachloropentane, tributyl phosphate, Chlorinated alkanols and chlorinated alkanoyl compounds.

  Thus, in embodiments of the invention, the product 1,1,1,3-tetrachloropropane is one of about 500 ppm or less, about 200 ppm or less, about 100 ppm or less, about 50 ppm or less, about 20 ppm or less, or about 10 ppm or less. Or more of that compound.

  For the avoidance of doubt, when the purity of a composition or substance is expressed in percent or ppm, this is weight percent / ppm (mass) unless otherwise stated.

  As mentioned above, the prior art does not disclose or teach a method for producing such high purity chlorinated alkanes that control the overall range of potential impurities. Therefore, according to the further aspect of this invention, said high purity chlorinated alkane composition is provided.

Alkylation process

First distillation process

Aqueous catalyst recovery process

Second distillation process

Examples The invention is further illustrated in the following examples.

Example 1 Demonstration of Catalytic Performance of a Catalyst Recovered Using Aqueous Treatment Ethene and carbon tetrachloride are either i) a catalyst recovered from the reaction mixture using conventional distillation methods, or ii) the invention described in this disclosure 1,1,3-tetrachloropropane was produced by reacting in the presence of catalyst recovered from the reaction mixture using an aqueous treatment process of The reaction mixture is generally added as a by-product in the presence of telomerization reaction between 1,1,1,3-tetrachloropropane (present in the recycle stream) and tetrachloropentane (carbon tetrachloride and ethene). Formed chlorinated alkane impurities).

  These test examples show that the performance of the catalyst when using an aqueous treatment step to recover the catalyst is sufficiently high compared to the catalyst recovered using conventional distillation methods.

For simplicity, the following terms are used in the examples described below:
TeCM: Tetrachloromethane,
TeCPa: 1,1,1,3-tetrachloropropane,
TeCPna: tetrachloropentane,
Bu ₃ PO ₄ : Tributyl phosphate.

  The progress of the reaction was monitored using Gas chromatography.

Batch Array A 405 ml volume stainless steel autoclave equipped with a stirrer, thermowell for temperature measurement, and sampling tube (with valve) was filled and closed with the reaction mixture described below. Heat was applied by an oil bath placed on a magnetic (heating) stirrer. Ethene was supplied by a copper capillary tube from a 10 l cylinder placed on the balance. The gas atmosphere in the autoclave was replaced by ethene flushing. After pressurizing to 5 bar with ethene, the autoclave was heated to 105 ° C. and then the ethene feed was opened to the autoclave. The ethene feed was manually controlled for the first 10 minutes (so as to maintain the reaction temperature at 120 ° C.) and then maintained at a constant pressure of 9 bar. The reaction was allowed to proceed for a predetermined time. The reactor was then cooled and the reaction mixture was withdrawn (the previously depressurized reactor was opened).

Comparative Examples 1-1 and 1-3 and Examples 1-2, 1-4 and 1-5
In the first example, the distillation residue was used directly as a reuse catalyst (Comparative Example 1-1). In the second example, the distillation residue was extracted with 5% hydrochloric acid, and the filtered organic fraction was used as a catalyst (Example 1-2).

Comparative Example 1-1
90.1 g of distillation residue containing 63.7% TeCPa, 22.8% TeCPna, and 7.49% Bu ₃ PO ₄ was mixed with 400 g TeCM. The mixture was then introduced into an autoclave supplemented with 5.0 g of iron. After flushing with ethene, the mixture was heated to 110 ° C. in an autoclave. At this temperature and a pressure of 9 bar ethene, the reaction mixture was reacted for 4.5 hours. The first sample was obtained after 3 hours. The concentration of residual TeCM at the end of the experiment was 19.7% (33.0% after 3 hours).

Example 1-2
90.1 g of distillation residue containing 63.7% TeCPa, 22.8% TeCPna, and 7.49% Bu ₃ PO ₄ was extracted with 370 g of 5% HCl. The lower organic phase was filtered and mixed with 400 g TeCM. The mixture was then introduced into an autoclave supplemented with 5.0 g of iron. After flushing with ethene, the mixture was heated to 110 ° C. in an autoclave. At this temperature and a pressure of 9 bar ethene, the reaction mixture was reacted for 4.5 hours. The first sample was obtained after 3 hours. The concentration of residual TeCM at the end of the experiment was 5.5% (24.6% after 3 hours).

Comparative Example 1-3
Comparative Example 1-3 was carried out using the same conditions as those used in Comparative Example 1-1, except that different concentrations of tetrachloromethane and tributyl phosphate were used.

Examples 1-4 and 1-5
Examples 1-4 and 1-5 were performed using the same conditions as used in Example 1-2, except that different concentrations of tetrachloromethane and tributyl phosphate were used.

  The results of Comparative Examples 1-1 and 1-2, and Comparative Examples 1-3, 1-4, and 1-5 are shown in the following table. As can be seen, the proportion of tetrachloromethane converted to 1,1,1,3-tetrachloropropane was greater than that of Comparative Examples 1-1 and 1-3 as in Examples 1-2, 1-4, and 1 -5 is high enough to show that the performance of the aqueous treatment step in recovering the catalyst has a significant positive impact on the system. This is due to the high feasibility of the catalyst recovered from the distillation residue and also potentially of impurities (eg oxygenated impurities) from the reaction mixture (which may otherwise slow the reaction). This is for removal.

Continuous arrangement The same stainless steel autoclave as described above for the batch experiment was used as a stirred flow continuous reactor. The reactor was initially filled with about 455 g of reaction mixture. After pressurizing to 5 bar with ethene, the autoclave was heated to 105 ° C., and then the ethene supply to the autoclave was opened to start continuous supply of raw materials and continuous extraction of the reaction mixture.

  The raw material solution containing the dissolved catalyst was supplied from the stainless steel tank to the autoclave. A tank was placed above the reactor and therefore a pump was used to feed the reactor. The reactor and tank were in an ethene atmosphere distributed by a copper capillary from the cylinder, with conditions in the cylinder selected to avoid initiation of the reaction. Sampling of the reaction mixture was performed with a sampling tube every 5 minutes. To monitor the course of the reaction, the vessel containing the raw material and the dissolved catalyst, the ethene cylinder, and the extracted reaction mixture were weighed. The reaction mixture was collected for 1 hour. Thereafter, the collection container is replaced.

Comparative Examples 1-6 and 1-8 and Examples 1-7 and 1-9
A continuous experiment comparing the activity of the recycled catalyst (ie, distillation residue) was performed with and without an aqueous treatment step. In the first case, the distillation residue was used directly as a recycled catalyst (Comparative Example 1-6). In the latter case, after aqueous treatment of the distillation residue with 5% HCl, the reaction mixture was used as a feed containing recycled catalyst (Examples 1-4 and 1-5).

Comparative Example 1-6
587.5 g of distillation residue containing 63.7% TeCPa, 22.8% TeCPna, and 7.49% Bu ₃ PO ₄ was mixed with 2200 g TeCM. This mixture contained 78.7% TeCM, 11.8% TeCPa, 5.8% TeCPna. This mixture was used as the feed stream for continuous sequencing. The reaction vessel constituting the autoclave was filled with the reaction mixture and 8 g of unused iron. The reaction was carried out at 110 ° C. with a pressure of 9 bar ethene. The residence time was 2.7 hours. During the reaction, the amount of reacted TeCM was 75-76%.

Example 1-7
587.5 g of distillation residue containing 63.7% TeCPa, 22.8% TeCPna, 7.49% Bu ₃ PO _{4 is taken} to 1001.5 g boiling 5% HCl over 1.5 hours. It was dripped. This mixture was then stripped. The organic phase was collected from the top product and the aqueous phase was returned as reflux. Distillation was completed 1 hour after all of the distillation residue was added. The stripped residue was diluted with 200 g TeCM and then separated in a separatory funnel. The lower organic phase was filtered and combined with the distilled residue and mixed with 2000 g TeCM. This mixture contained 81.2% TeCM, 10.8% TeCPa, and 5.3% TeCPna. It was used as a feed stream for a continuous sequence of experiments. The reaction vessel (autoclave) was filled with the older reaction mixture and 8 g of unused iron. The reaction was carried out at 110 ° C. and a pressure of 9 bar ethene. The residence time was 2.7 hours / flow rate. During the reaction time, the amount of reacted TeCM was 83-85%.

Comparative Example 1-8
Comparative Example 1-8 was carried out using the same conditions as those used in Comparative Example 1-6 except that different concentrations of tetrachloroethane and tributyl phosphate were used.

Example 1-9
Example 1-9 was performed using the same conditions as used in Example 1-7, except that different concentrations of tetrachloromethane and tributyl phosphate were used.

Example 2-Preparation of high purity 1,1,1,3-tetrachloropropane Alkylation step (Figure 1), first distillation step (Figure 2), aqueous catalyst recovery step (Figure 3), and second distillation According to the method of the present invention including the step (FIG. 4), 1,1,1,3-tetrachloropropane having a high purity can be obtained. However, all of these steps will be understood that it is not essential to obtain a high-purity C _{3 ~ 6} alkanes according to the method of the present invention.

  In the alkylation process shown in FIG. 1, ethene and granular iron are fed to continuous stirred tank reactor 3 via lines 1 and 2. Ethene is introduced in gaseous form into the continuous stirred tank reactor 3 via a dip tube equipped with a nozzle. A controlled feed of granular iron is introduced into the continuous stirred tank reactor 3.

  Granular iron is fed intermittently to the continuous stirred tank reactor 3 using a controlled feed. Since the granular iron dissolves in the reaction mixture as the alkylation reaction proceeds, continuous addition of granular iron is used. It has been found that optimal results are obtained in this example by maintaining the presence of particulate iron in the reaction mixture by addition of 1-2% by weight of the reaction mixture in the primary alkylation zone. This results in a reaction mixture extracted from the primary alkylation zone having a dissolved iron content of 0.2-0.3% by weight of the reaction mixture.

  Carbon tetrachloride is fed in liquid form to the continuous stirred tank reactor 3 via line 12. In the embodiment shown, a carbon tetrachloride stream is used to collect gaseous ethene extracted from the reaction mixture. However, the use of such carbon tetrachloride is not essential to the present invention, and a fresh carbon tetrachloride feed, either alone or as the main source of carbon tetrachloride, can be fed to the reactor 3.

  A tributyl phosphate / ferric chloride catalyst is also fed to the continuous stirred tank reactor 3 via line 12. The tributyl phosphate present in this stream is partially obtained from the aqueous treatment process shown in FIG. 3 (and will be discussed in more detail below), with the remainder being given as unused tributyl phosphate added to the system. It is done. The stream in line 12 additionally contains a haloalkane extractant.

  In the embodiment shown, a single primary alkylation zone is used and placed in the continuous stirred tank reactor 3. Of course, if necessary, multiple primary alkylation zones can be used, for example using one or more continuous stirred tank reactors that can operate in parallel and / or in series. Can do.

The primary alkylation zone is operated at pressures below ambient pressure (5-8 bar gauge) and elevated temperatures (105 ° C.-110 ° C.) with a residence time of 100-120 minutes. These conditions are selected to yield carbon tetrachloride and ethene to form 1,1,1,3-tetrachloropropane in the alkylation reaction. However, it has been found that the total conversion of carbon tetrachloride to 1,1,1,3-tetrachloropropane is undesirable because it also results in the formation of undesirable impurities. Therefore, to control the degree of fourth carbon tetrachloride conversion to chlorinated alkanes C _{3 ~ 6} purpose, in this embodiment of the present invention, it does not allow the progression of more than 95%. Use of reaction conditions that do not favor the total conversion of carbon tetrachloride to 1,1,1,3-tetrachloropropane by controlling the progress of the alkylation reaction by controlling the residence time of the reaction mixture in a continuously stirred tank reactor Partially achieved by

including i) unreacted carbon tetrachloride and ethene, ii) 1,1,1,3-tetra-chloropropane (C _{3 ~ 6} chlorinated alkane of interest in the present embodiment), and iii) tributyl phosphate / iron catalyst chloride The reaction mixture is extracted from the primary alkylation zone (continuous stirred tank reactor 3) and fed to the plug / flow reactor 4 (where the main alkylation zone is located).

  Since the reaction mixture is extracted so as not to extract the particulate iron catalyst present in the primary alkylation zone 3, the reaction mixture is substantially free of particulate material. Further, in the illustrated embodiment, no additional catalyst is added to the plug / flow reactor 4 even though the plug / flow reactor 4 can include a catalyst bed. In addition, no further ethene is added to the plug / flow reactor 4.

  In the embodiment shown, the operating pressure in the main alkylation zone 4 is the same as in the primary alkylation zone 3. The residence time of the reaction mixture was about 30 minutes, which in the embodiment shown was sufficient to use up substantially all of the ethene present during the reaction. Of course, it will be appreciated that different reactor types and operating conditions, different residence times may be optimal.

  When the determined optimum residence time of the reaction mixture has been reached in the main alkylation zone, the reaction mixture is extracted from it via line 5 and fed to the flash evaporation vessel 6 while maintaining high pressure and temperature. . In this vessel, the extracted reaction mixture was depressurized to ambient pressure. This pressure drop causes the ethene present in the reaction mixture to evaporate. A rich mixture of 1,1,1,3-tetrachloropropane substantially free of ethene is extracted from the flash vessel via line 7 and subjected to the distillation process shown in FIG. 2 and discussed in more detail below. Provide.

  Evaporated ethene is extracted from the flash vessel 6 via line 8 and fed via a condenser 9. Ethene is then fed to absorption column 11 via line 10 where tributyl phosphate / iron chloride catalyst and carbon tetrachloride recovered from the reaction mixture in the aqueous treatment step shown in FIG. 3 and discussed in more detail below. Contact with the stream. The recovered catalyst / carbon tetrachloride stream 13 is passed to cooler 14 and then fed to absorption column 11 via line 15.

  The cooled carbon tetrachloride / catalyst stream through the absorption column 11 has the effect of collecting ethene there. The resulting liquid stream of carbon tetrachloride / catalyst / ethene is then returned to the continuous stirred tank reactor 3.

  As can be seen from FIG. 1, the illustrated embodiment includes an advantageous ethene recirculation loop for several reasons. First, almost all use of ethene is achieved, so the amount of ethene loss from the system is very low. In addition, the energy requirements of the components of the ethene recirculation system are low. Furthermore, the amount of ethene loss from the system is also very low, which means that the environmental load is reduced.

  Referring to FIG. 2, a batch operating in communication with vacuum distillation column 104 is a rich mixture of 1,1,1,3-tetrachloropropane extracted from the flash vessel indicated by reference numeral 6 in FIG. A distillation boiler 102 is supplied via a line 101. The distillation boiler is operated at a temperature of 90 ° C to 95 ° C. The chloroalkane present in the mixture fed to the boiler 102 is evaporated and a light end stream 110.1, a carbon tetrachloride stream 110.2, using a distillation column 104 (and downstream condenser 106 and reflux distributor 108), Separated into tetrachloroethene stream 110.3 and purified 1,1,1,3-tetrachloropropane product stream 110.4.

  The light end and tetrachloroethene streams 110.1, 110.3 can be used in the production of carbon tetrachloride, advantageously minimizing the production of waste products. This can be achieved through the use of a high temperature chlorinolysis process.

  The carbon tetrachloride stream 110.2 is returned to the continuous stirred tank reactor 103. The purified 1,1,1,3-tetrachloropropane product stream 110.4 can be extracted from the system and stored for transport, or pure 1,1,1,3-tetra It can be used in downstream processes that require chloropropane.

  A rich mixture of 1,1,1,3-tetrachloropropane including the catalyst is extracted as a residue from the boiler 102 via the line 103 and subjected to the catalyst recovery step shown in FIG.

  In this process, a rich mixture of 1,1,1,3-tetrachloropropane is fed to batch distillation boiler 204 via line 202 along with the weak (1-5%) hydrochloric acid solution from line 201.

  Advantageously, the water present in the acid solution deactivates the catalyst system and protects it from thermal damage. This makes it possible to recover the catalyst system from a rich mixture of 1,1,1,3-tetrachloropropane, which is easily reactivated after recovery, in the alkylation process without significant loss of catalytic activity. Can be reused.

  The batch distillation boiler is operated at a temperature of about 100 ° C. to produce a gaseous mixture containing 1,1,1,3-tetrachloropropane and water vapor.

  The gaseous mixture produced in boiler 204 is then subjected to steam distillation (or steam stripping) of crude 1,1,1,3-tetrachloropropane in column 210 coupled to boiler 204. Crude 1,1,1,3-tetrachloropropane is extracted from distillation column 210 via line 211, condensed by condenser 212, and fed to reflux liquid-liquid separator 214 via line 213. As shown in more detail in FIG. 4 and discussed in more detail below, water from the gaseous mixture is returned to the distillation column 210 via line 215, with a portion of line 216 for further distillation steps. Take out through.

  The operating temperature of the boiler 204 is then lowered to stop steam stripping, resulting in condensation of water vapor present therein. This resulted in the formation of a biphasic mixture comprising an aqueous phase and an organic phase comprising a catalyst system, which was not subjected to steam stripping. To facilitate the extraction of the organic phase, a haloalkane extractant (in this case 1,1,1,3-tetrachloropropane) was added to boiler 204 via line 203 to increase the volume of this phase.

  Extraction of the organic phase from the biphasic mixture is accomplished by sequentially extracting the phases from the boiler 204 via line 205. The organic phase is extracted from boiler 204 via line 205 and filtered (206). Filter cake is removed from filter 206 via line 207. The organic phase is extracted via line 208 and in this embodiment is returned to the primary alkylation zone, particularly via line 13 of FIG. 1, as shown in FIG. The aqueous phase is extracted via line 205, filtered (206) and discarded via line 209.

  The stripped crude 1,1,1,3-tetrachloropropane product is subjected to a further distillation step as shown in FIG. In this step, the crude product is fed to distillation boiler 302 via line 301. The boiler 302 communicates with the distillation column 304. In distillation column 304 (and associated downstream equipment, condenser 306 and reflux distributor 308), the evaporated chlorinated organic compounds present in the crude 1,1,1,3-tetrachloropropane were purified 1, Separated into 1,1,3-tetrachloropropane product stream 310.1 and chlorinated pentane / pentene stream 310.2.

  The chlorinated pentane / pentene stream 310.2 can be used in the production of carbon tetrachloride, advantageously minimizing the production of waste products. This can be achieved through the use of a high temperature chlorinolysis process.

  Purified 1,1,1,3-tetrachloropropane product stream 310.1 can be extracted from the system and combined with the main product stream (identified as reference number 110.4 in FIG. 2). The product can be stored for transport or used in downstream processes requiring pure 1,1,1,3-tetrachloropropane as starting material.

  The heavy end residue extracted from boiler 302 via line 303 is discarded or further processed.

  Using the equipment and process conditions outlined above, 2635 kg of carbon tetrachloride (CTC, 99.97% purity) was continuously treated with an average time loading of 78.2 kg / h and 1,1,1 , 3-Tetrachloropropene (1113TeCPa) was prepared. The basic parameters of the disclosed process carried out according to Example 2 are:

  The total impurity profile of the purified product of the above embodiment is presented in the table below. Note that the numbers are given as a weighted average of the product profiles outlined in line 110.4 in FIG. 2 and line 310.1 in FIG.

Example 3: Effect of the starting material: product molar ratio in the reaction mixture on selectivity These examples were outlined above in "Sequential Sequence" in Example 1 except where otherwise noted. Performed using apparatus and method. (In this case, 1,1,1,3-tetra-chloropropane) C _{3 ~ 6} chlorinated alkane products in the reaction mixture: four molar ratio of carbon tetrachloride, the residence time of the main reaction mixture in the alkylation zone Were controlled at different concentrations. The temperature was maintained at 110 ° C. and the pressure was maintained at 9 Bar. The selectivity for the desired product is reported in the table below.

  As can be seen from this example, if the product: starting material molar ratio exceeds 95: 5 when the process is operated continuously, there is a noticeable reduction in selectivity to the desired product. .

Example 4: Effect of the starting material: product molar ratio in the reaction mixture on selectivity These examples refer to the description with reference to Example 2 above, except where otherwise noted. This was carried out using the apparatus and method shown in 1. (In this case, 1,1,1,3-tetra-chloropropane) C _{3 ~ 6} chlorinated alkane products in the reaction mixture: four molar ratio of carbon tetrachloride, primarily by controlling the feed rate of the ethylene starting material Were controlled at different concentrations. The temperature was a constant 110 ° C. The selectivity for the desired product is reported in the table below.

  As can be seen from this example, if the product: starting material molar ratio exceeds 95.5 when the process is operated continuously, there is a noticeable reduction in selectivity to the desired product. .

Example 5: Effect of Raw Material Purity These examples were carried out using the apparatus and method shown in FIG. 2 with reference to the description accompanying Example 2 above, except where otherwise noted. Trial 5-1 is a stream obtained from stream 110.4 in FIG. Trials 5-2 to 5-5 are alternative examples obtained using the same equipment and method but with different purity raw materials. Although the following data used lower purity raw materials in trials 5-2 to 5-5, this advantageously has a significant impact on the purity of the product when obtained from the process of the present invention. Indicates not to give.

Example 6: Combination of CSTR and Plug Flow These examples were performed using the apparatus and method shown in FIG. 1 with reference to the description accompanying Example 2 above, except where otherwise noted. . The efficiency of the reaction in the second plug flow reactor (reference number 4 in FIG. 1) was evaluated. Two trials were performed with different amounts of dissolved ethylene at the inlet of the plug flow reactor operating at the same temperature (110 ° C.) as the main CSTR reactor (reference number 3 in FIG. 1). The results are shown in the table below.

  As can be seen from this example, there is 75-93% ethylene conversion in the plug flow reactor. Thus, when using a plug flow reactor, there is more efficient ethylene utilization in the reaction section. The continuous plug flow reactor operates the CSTR reactor at optimal pressure without the need for complicated and uneconomic ethylene recovery processes. The continuous plug reactor thus effectively controls ethylene usage in a closed loop.

Example 7: Troublesome decomposition of catalyst ligands during conventional distillation A fractionation apparatus was constructed consisting of a 2 liter glass distillation 4-neck flask equipped with a condenser, thermometer, warm bath, and vacuum pump system. Initially, a distillation flask was filled with 1976 grams of the reaction mixture obtained using the apparatus and method shown in FIG. 1 and described with the description of Example 2 above.

  During distillation, the pressure was gradually reduced from an initial pressure of 100 mmHg to a final pressure of 6 mmHg. During this period, 1792 grams of distillate (in different fractions) was extracted. During distillation there was visible HCl gas formation, and also chlorobutane (decomposition product from tributyl phosphate ligand) was formed in a significant amount, i.e. 1-19% with respect to the distillation fraction. Once these observations were made, the distillation was discontinued and the distillation residue was weighed and analyzed and found to have a tetrachloropropane content of 16%. It was no longer possible to continue distillation without significant degradation of the tributyl phosphate ligand.

Claims (31)

And to produce a C _{3 ~ 6} chlorinated alkanes with alkenes and quaternary reaction mixture giving a reaction mixture containing carbon tetrachloride in major alkylation zone, and extracting a portion of the reaction mixture from the main alkylation zone the including a method for producing a C 3 _{~ 6} chlorinated alkanes,
The concentration of C _{3 ~ 6} chlorinated alkane in the reaction mixture in a) said primary alkylation zone, said C _{3 ~ 6} chlorinated alkanes alkylation zone reaction mixture extracted from the molar ratio of carbon tetrachloride Maintaining a concentration not exceeding 95: 5 when the main alkylation zone is in continuous operation, and / or b) the reaction mixture extracted from said main alkylation zone additionally comprises an alkene Dealkene from which at least about 50% by weight or more of the alkene present in the reaction mixture is extracted, and at least about 50% of the extracted alkene is returned to the reaction mixture provided in the main alkylation zone. And / or c) a reaction mixture present in the main alkylation zone and extracted from the main alkylation zone The reaction mixture additionally containing a catalyst and extracted from the main alkylation zone is contacted with an aqueous medium in the aqueous treatment zone to form a biphasic mixture, and the organic phase containing the catalyst is removed from the biphasic mixture. The method used for the aqueous treatment process to extract.   The method of claim 1, wherein the alkene is ethene, propene, and / or chlorinated propene. The C _{3 ~ 6} alkane, 1,1,1,3 tetra-chloropropane A method according to claim 1 or 2.   The process according to any one of claims 1 to 3, wherein a catalyst is added to the reaction mixture.   The method according to claim 1, wherein the catalyst is a metal-based catalyst, optionally a metal-based catalyst further comprising an organic ligand.   6. The method of claim 5, wherein the organic ligand is an alkyl phosphate, such as triethyl phosphate and / or tributyl phosphate.   The method of any one of claims 1-6, wherein the primary alkylation zone is operated at a temperature of about 30C to about 160C.   8. The method of any one of claims 1-7, wherein the primary alkylation zone is operated at a temperature of about 80C to about 120C.   9. A process according to any one of the preceding claims, wherein the reaction mixture is formed in the main alkylation zone. The alkene and carbon tetrachloride are contacted in the primary alkylation zone to form a reaction mixture, the reaction mixture is then extracted from the primary alkylation zone, fed to the main alkylation zone, and from the main alkylation zone C _{3 ~ 6} chlorinated alkanes present in the reaction mixture which is extracted: four ratio chloride carbon, C _{3 ~ 6} chlorinated alkanes present in the reaction mixture obtained from the primary alkylation zone: carbon tetrachloride 9. The method according to any one of claims 1 to 8, wherein the method is greater than the ratio.   The method of claim 10, wherein the primary alkylation zone is operated at the same or different pressure as the primary alkylation zone.   12. A method according to claim 10 or 11, wherein the primary alkylation zone is operated in a continuous process.   13. A process according to any one of claims 10 to 12, wherein no alkene or solid metal catalyst is fed to the main alkylation zone other than what is present in the reaction mixture fed to the main alkylation zone.   14. A process according to any one of claims 10 to 13, wherein the reaction mixture obtained from the primary alkylation zone and fed to the main alkylation zone is substantially free of solid metal catalyst.   15. A process according to any one of the preceding claims, wherein the dealkenylation step comprises feeding the reaction mixture extracted from the main alkylation zone to a distillation zone that distills the alkene from the reaction mixture. .   16. The process of claim 15, wherein the alkene distilled from the reaction mixture is obtained in a stream rich in the alkene.   The process according to claim 15 or 16, wherein the distillation zone is an evaporation zone for evaporating alkene from the reaction mixture. Wherein before the aqueous treatment step, by distillation in Optionally, said about 30 wt% to about 85% by weight of C _{3 - 6} chlorinated alkanes present in the reaction mixture extracted from the primary alkylation zone 18. A process according to any one of claims 1 to 17, which is removed from the reaction mixture.   18. A method according to any one of claims 1 to 17, wherein the aqueous medium comprises dilute acid, optionally dilute hydrochloric acid. The majority of C _{3 ~ 6} chlorinated alkanes present in said aqueous treatment reaction mixture fed to the zone, the optional mixtures formed in the aqueous treatment zone extracted by distillation, according to claim 1 The method of any one of -19. Further comprising a method according to any one of claims 1 to 20 the step of supplying carbon tetrachloride and / or C _{3 ~ 6} chlorinated alkanes to said aqueous treatment zone.   The method of any one of claims 1-21, wherein a biphasic mixture is formed in the aqueous treatment zone.   23. A process according to any one of the preceding claims, wherein the organic phase is extracted from the biphasic mixture by sequential phase separation. Supplying steam to said aqueous treatment zones, and / or steam to thereby form in situ by boiling the water present in the aqueous treatment zone, a gaseous mixture containing C 3 _{~ 6} chlorinated alkanes and water vapor a is, to produce a gaseous mixture capable of distilling a C _{3 ~ 6} chlorinated alkanes from the gaseous mixture, the method according to any one of claims 1 to 23. Can be obtained by the method according to any one of claims 1 to 24, the composition comprising a C 3 _{~ 6} chlorinated alkanes. About 99.0% or more, about 99.5% or more, about 99.7% or more, about 99.8% or more, or about 99.9% or more of chlorinated alkanes,
· Less than about 2000 ppm, less than about 1000 ppm, less than about 500 ppm, less than about 200 ppm, or about 100ppm less chlorinated alkane impurities (i.e., C _{3 ~} chlorinated alkane compounds other than ₆ chlorinated alkane of interest),
Less than about 2000 ppm, less than about 1000 ppm, less than about 500 ppm, less than about 200 ppm, or less than about 100 ppm, chlorinated alkene compound;
Less than about 2000 ppm, less than about 1000 ppm, less than about 500 ppm, less than about 200 ppm, or less than about 100 ppm oxygenated organic compound,
Less than about 2000 ppm, less than about 1000 ppm, less than about 500 ppm, less than about 200 ppm, or less than about 100 ppm brominated compound;
Less than about 1000 ppm, less than about 500 ppm, less than about 200 ppm, less than about 100 ppm, less than about 50 ppm, or less than about 20 ppm water;
Less than about 500 ppm, less than about 200 ppm, less than about 100 ppm, less than about 50 ppm, or less than about 20 ppm, and / or less than about 500 ppm, less than about 200 ppm, less than about 100 ppm, less than about 50 ppm, or less than about 20 ppm 26. The composition of claim 25, comprising a catalyst promoter of: The C _{3 ~ 6-chloro-alkane,} 1,1,1,3 tetra-chloropropane A composition according to claim 26. - about 99.0% or more, about 99.5%, about 99.7% or more, about 99.8% or more, or about 99.9% or more C _{3 ~ 6} chlorinated alkanes,
· Less than about 2000 ppm, less than about 1000 ppm, less than about 500 ppm, less than about 200 ppm, or about 100ppm less chlorinated alkane impurities (i.e., C _{3 ~} chlorinated alkane compounds other than ₆ chlorinated alkane of interest),
Less than about 2000 ppm, less than about 1000 ppm, less than about 500 ppm, less than about 200 ppm, or less than about 100 ppm, chlorinated alkene compound;
Less than about 2000 ppm, less than about 1000 ppm, less than about 500 ppm, less than about 200 ppm, or less than about 100 ppm oxygenated organic compound,
Less than about 2000 ppm, less than about 1000 ppm, less than about 500 ppm, less than about 200 ppm, or less than about 100 ppm brominated compound;
Less than about 1000 ppm, less than about 500 ppm, less than about 200 ppm, less than about 100 ppm, less than about 50 ppm, or less than about 20 ppm water;
Less than about 500 ppm, less than about 200 ppm, less than about 100 ppm, less than about 50 ppm, or less than about 20 ppm, and / or less than about 500 ppm, less than about 200 ppm, less than about 100 ppm, less than about 50 ppm, or less than about 20 ppm compositions containing from catalyst promoter, comprising a C 3 _{~ 6} chlorinated alkanes. C _{3 ~ 6-chloro-alkane,} a 1,1,1,3 tetrachloropropane The composition of claim 28.   30. Use of the composition according to any one of claims 25 to 29 as a raw material in the synthesis of halogenated alkenes or halogenated alkanes.   Use according to claim 30, wherein the halogenated alkene or halogenated alkane is a fluorinated and / or chlorinated alkene or a fluorinated and / or chlorinated alkane.

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